U.S. patent number 6,358,892 [Application Number 09/176,278] was granted by the patent office on 2002-03-19 for polyalkylene succinimides and post-treated derivatives thereof.
This patent grant is currently assigned to Chevron Chemical Company. Invention is credited to James J. Harrison, William R. Ruhe, Jr..
United States Patent |
6,358,892 |
Harrison , et al. |
March 19, 2002 |
Polyalkylene succinimides and post-treated derivatives thereof
Abstract
A succinimide composition is prepared by reacting a mixture of
an alkenyl or alkylsuccinic acid derivative, an unsaturated acidic
reagent copolymer, and a polyamine under reactive conditions; then
treating the reaction product with either a cyclic carbonate or a
linear mono- or polycarbonate or boron compound under reactive
conditions. The alkenyl or alkyl substituent of the alkenyl or
alkylsuccinic acid derivative has a Mn of from 1800 to 3000. The
unsaturated acidic reagent copolymer has a Mn of from 2000 to 4800,
and is a copolymer of an unsaturated acidic reagent and an olefin
having an average of from 14 to 30 carbon atoms. The polyamine has
at least three nitrogen atoms and 4 to 20 carbon atoms. The mixture
contains from 1.5 to 10 equivalents of the alkenyl or alkylsuccinic
acid derivative per equivalent of unsaturated acidic reagent
copolymer and from 0.4 to 1.0 moles of polyamine per equivalent of
alkenyl or alkylsuccinic acid derivative plus unsaturated acidic
reagent copolymer.
Inventors: |
Harrison; James J. (Novato,
CA), Ruhe, Jr.; William R. (Benecia, CA) |
Assignee: |
Chevron Chemical Company (San
Ramon, CA)
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Family
ID: |
24532126 |
Appl.
No.: |
09/176,278 |
Filed: |
January 27, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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631648 |
Apr 9, 1996 |
5716912 |
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566231 |
Dec 1, 1995 |
5821205 |
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Current U.S.
Class: |
508/192; 508/222;
508/291; 526/262 |
Current CPC
Class: |
C10M
129/52 (20130101); C10M 161/00 (20130101); C10L
1/143 (20130101); C08F 8/14 (20130101); C10M
129/84 (20130101); C10L 1/238 (20130101); C10M
133/56 (20130101); C10M 149/06 (20130101); C10L
1/303 (20130101); C10L 1/236 (20130101); C08F
8/00 (20130101); C10L 10/04 (20130101); C08F
8/32 (20130101); C10L 10/08 (20130101); C10L
1/234 (20130101); C08F 8/48 (20130101); C10L
1/221 (20130101); C10L 1/2364 (20130101); C10L
1/2368 (20130101); C10M 139/00 (20130101); C10L
1/2366 (20130101); C10M 159/12 (20130101); C10M
159/12 (20130101); C10M 133/56 (20130101); C10M
129/52 (20130101); C10M 129/84 (20130101); C10M
139/00 (20130101); C08F 8/48 (20130101); C08F
8/32 (20130101); C08F 210/14 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
222/06 (20130101); C08F 8/48 (20130101); C08F
8/32 (20130101); C08F 222/08 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
212/08 (20130101); C08F 8/32 (20130101); C08F
222/06 (20130101); C08F 8/32 (20130101); C08F
210/02 (20130101); C08F 8/32 (20130101); C08F
222/06 (20130101); C08F 8/32 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
222/06 (20130101); C08F 8/32 (20130101); C08F
218/08 (20130101); C08F 218/08 (20130101); C08F
8/00 (20130101); C08F 8/32 (20130101); C08F
218/08 (20130101); C08F 8/00 (20130101); C08F
8/32 (20130101); C08F 222/06 (20130101); C08F
222/06 (20130101); C08F 8/00 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
222/06 (20130101); C08F 8/00 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
210/14 (20130101); C08F 8/00 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
212/08 (20130101); C08F 8/00 (20130101); C08F
8/48 (20130101); C08F 8/32 (20130101); C08F
222/08 (20130101); C08F 8/32 (20130101); C08F
210/02 (20130101); C08F 8/32 (20130101); C08F
218/08 (20130101); C08F 8/00 (20130101); C08F
8/32 (20130101); C08F 222/06 (20130101); C10M
2215/28 (20130101); C10L 1/1824 (20130101); C10M
2217/06 (20130101); C10M 2227/066 (20130101); C10L
1/1608 (20130101); C10M 2215/04 (20130101); C10N
2040/25 (20130101); C10M 2227/061 (20130101); C08F
2810/50 (20130101); C10L 1/2493 (20130101); C10M
2207/32 (20130101); C10L 1/1616 (20130101); C10L
1/2383 (20130101); C10M 2227/00 (20130101); C10N
2040/28 (20130101); C08F 2800/20 (20130101); C10M
2227/06 (20130101); C10M 2217/024 (20130101); C10N
2070/02 (20200501); C10M 2217/046 (20130101); C10M
2227/062 (20130101); C10N 2040/255 (20200501); C10L
1/2691 (20130101); C10N 2040/251 (20200501); C10M
2215/26 (20130101); C10M 2227/063 (20130101); C10M
2207/142 (20130101); C10M 2227/065 (20130101); C10M
2217/024 (20130101); C10M 2217/024 (20130101); C08F
210/14 (20130101) |
Current International
Class: |
C10L
1/238 (20060101); C10M 149/00 (20060101); C08F
8/00 (20060101); C10L 1/22 (20060101); C10L
1/234 (20060101); C10L 1/30 (20060101); C08F
8/32 (20060101); C10L 10/00 (20060101); C10L
1/236 (20060101); C10M 149/06 (20060101); C10L
1/10 (20060101); C10M 133/00 (20060101); C10M
159/12 (20060101); C10M 133/56 (20060101); C10M
159/00 (20060101); C10M 161/00 (20060101); C10L
1/14 (20060101); C10L 1/16 (20060101); C10L
1/18 (20060101); C10L 1/24 (20060101); C10L
1/26 (20060101); C10M 133/44 (); C10M 149/10 () |
Field of
Search: |
;44/330,331,346,317
;508/192,222 ;526/262 ;558/286,295,297 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0682102 |
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Nov 1965 |
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EP |
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0072645 |
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Feb 1983 |
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EP |
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0146162 |
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Jun 1985 |
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EP |
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0657475 |
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Jun 1995 |
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EP |
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1488486 |
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Oct 1977 |
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GB |
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Other References
ES. Forbes and E.I. Neustadter "The Mechanism of Action of
Polyisobutenyl Succinmide Lubricating Oil Additives." (Tribology,
vol. 5, No. 2, pp. 72-77; Apr. 1972).* .
S.T. Roby, R.E. Kornbrekke and J.A. Supp, "Deposit Formulation in
Gasoline Engines, Part 2, Dispersant Effects on Sequence VE
Deposits." (Journal of the Society of Tribologists and Lubrication
Engineers, vol. 50, 12, 989-995; Dec. 1994)..
|
Primary Examiner: Medley; Margaret
Attorney, Agent or Firm: Stumpf; Walter L. Sheridan; Richard
J.
Parent Case Text
This application is a division of application U.S. Ser. No.
08/631,648, filed Apr. 9, 1996 and now U.S. Pat. No. 5,716,912,
which is a continuation-in-part of application U.S. Ser. No.
08/566,231, filed Dec. 1, 1995 and now U.S. Pat. No. 5,821,205,
both of which are incorporated by reference herein in their
entirety.
Claims
What is claimed is:
1. A post-treated polymer prepared by treating a polymer with a
cyclic carbonate or a linear mono- or poly-carbonate under reactive
conditions, wherein said polymer is prepared by reacting a mixture
under reactive conditions, wherein the mixture comprises:
(a) an alkenyl or alkylsuccinic acid derivative, wherein the
alkenyl or alkyl substituent has a Mn of from 1800 to 3000;
(b) an unsaturated acidic reagent copolymer of
(1) an unsaturated acidic reagent and
(2) an olefin having an average of from 14 to 30 carbon atoms,
wherein the copolymer has a Mn of from 2000 to 4800; and
(c) a polyamine having at least three nitrogen atoms and 4 to 20
carbon atoms; and
wherein said mixture contains from 1.5 to 10 equivalents of said
alkenyl or alkylsuccinic acid derivative per equivalent of said
unsaturated acidic reagent copolymer and from 0.4 to 1.0
equivalents of said polyamine per equivalent of alkenyl or
alkylsuccinic acid derivative plus unsaturated acidic reagent
copolymer.
2. The polymer of claim 1 wherein said cyclic carbonate is ethylene
carbonate.
3. A lubricating oil composition comprising a major amount of an
oil of lubricating viscosity and a minor amount of the polymer of
claim 1.
4. A concentrate comprising from 20 to 60 wt. % of the composition
of claim 1 and from 80 to 40 wt. % of an organic diluent.
5. A post-treated polymer prepared by treating a polymer under
reactive conditions with a boron compound selected from the group
consisting of boron oxide, boron halide, boric acid, and esters of
boric acid, wherein said polymer is prepared by reacting a mixture
under reactive conditions, wherein the mixture comprises:
(a) an alkenyl or alkylsuccinic acid derivative, wherein the
alkenyl or alkyl substituent has a Mn of from 1800 to 3000;
(b) an unsaturated acidic reagent copolymer of
(1) an unsaturated acidic reagent and
(2) an olefin having an average of from 14 to 30 carbon atoms,
wherein the copolymer has a Mn of from 2000 to 4800; and
(c) a polyamine having at least three nitrogen atoms and 4 to 20
carbon atoms; and
wherein said mixture contains from 1.5 to 10 equivalents of said
alkenyl or alkylsuccinic acid derivative per equivalent of said
unsaturated acidic reagent copolymer and from 0.4 to 1.0
equivalents of said polyamine per equivalent of alkenyl or
alkylsuccinic acid derivative plus unsaturated acidic reagent
copolymer.
Description
The present invention relates to novel compositions comprising
polyalkylene succinimides and post-treated derivatives of
polyalkylene succinimides. In a further aspect, the invention
relates to methods of preparing these compositions and their uses
as dispersants in lubricating oils and deposit inhibitors in
hydrocarbon fuels. In another aspect, the invention relates to
concentrates, lubricating oil compositions, and hydrocarbon fuel
compositions containing such novel compositions.
BACKGROUND OF THE INVENTION
Lubricating oil compositions for internal combustion engines
generally contain a variety of additives to reduce or control
deposits, wear, corrosion, etc. Similarly, liquid hydrocarbon fuels
for internal composition engines, at a minimum, contain additives
which control or reduce the formation of deposits. The present
invention is concerned with compositions useful as dispersants or
deposit inhibitors.
In lubricating oils, dispersants function to control sludge,
carbon, and varnish produced primarily by the incomplete oxidation
of the fuel, or impurities in the fuel, or impurities in the base
oil used in the lubricating oil composition. Dispersants also
control viscosity increase due to the presence of soot in diesel
engine lubricating oils.
Deposit inhibitors in fuel control or reduce engine deposits also
caused by incomplete combustion of the fuel. Such deposits can form
on the carburetor parts, throttle bodies, fuel injectors, intake
parts, and valves. Those deposits can present significant problems,
including poor acceleration and stalling, and increased fuel
consumption and exhaust pollutants.
One of the most effective class of lubricating oil dispersants and
fuel deposit inhibitors are polyalkylene succinimides. In some
cases, the succinimides have also been found to provide
fluid-modifying properties, or a so-called viscosity index credit,
in lubricating oil compositions. That results in a reduction in the
amount of viscosity index improver which would be otherwise have to
be used. A drawback of succinimide dispersants is that they have
generally been found to reduce the life of fluorocarbon elastomers.
In general, for a given succinimide dispersant, a higher nitrogen
content gives better dispersancy but poorer fluorocarbon elastomer
compatibility.
Therefore, as well as improving the dispersancy and VI credit
properties of polyalkylene succinimides, it would be desirable to
improve the fluorocarbon elastomer compatibility of such
dispersants. It would further be desirable to improve the stability
of polyalkylene succinimides, particularly hydrolytic stability and
shear stress stability. It would also be desirable to improve soot
dispersancy, especially where the lubricating oil is intended for
use in diesel engine crankcases.
Polyalkylene succinimides are generally prepared by the reaction of
the corresponding polyalkylene succinic anhydride with a polyalkyl
polyamine. Polyalkylene succinic anhydrides are generally prepared
by a number of well-known processes. For example, there is a
well-known thermal process (see, e.g., U.S. Pat. No. 3,361,673), an
equally well-known chlorination process (see, e.g., U.S. Pat. No.
3,172,892), a combination of the thermal and chlorination processes
(see, e.g., U.S. Pat. No. 3,912,764), and free radical processes
(see, e.g., U.S. Pat. Nos. 5,286,799 and 5,319,030). Such
compositions include one-to-one monomeric adducts (see, e.g., U.S.
Pat. Nos. 3,219,666 and 3,381,022), as well as "multiply adducted"
products, adducts having alkenyl-derived substituents adducted with
at least 1.3 succinic groups per alkenyl-derived substituent (see,
e.g., U.S. Pat. No. 4,234,435).
U.S. Pat. Nos. 3,361,673 and 3,018,250 describe the reaction of an
alkenyl- or alkyl-substituted succinic anhydride with a polyamine
to form alkenyl or alkyl succinimides lubricating oil dispersants
and/or detergent additives.
U.S. Pat. No. 4,612,132 teaches that alkenyl or alkyl succinimides
may be modified by reaction with a cyclic or linear carbonate or
chloroformate such that one or more of the nitrogens of the
polyamine moiety is substituted with a hydrocarbyl oxycarbonyl, a
hydroxyhydrocarbyl oxycarbonyl, or a hydroxy poly(oxyalkylene)
oxycarbonyl. These modified succinimides are described as
exhibiting improved dispersancy and/or detergency in lubricating
oils.
U.S. Pat. No. 4,747,965 discloses modified succinimides similar to
those disclosed in U.S. Pat. No. 4,612,132, except that the
modified succinimides is described as being derived from
succinimides having an average of greater than 1.0 succinic groups
per long chain alkenyl substituent.
The effect of the alkenyl-derived substituent's molecular weight on
the performance of succinimides as lubricating oil additives is
described in "The Mechanism of Action of Polyisobutenyl Succinimide
Lubricating Oil Additives," by E. S. Forbes and E. L. Neustadter
(Tribology, Vol. 5, No. 2, pp. 72-77 (April, 1972)). This article
discusses, in part, the effect of polyisobutenyl Mn on the
detergency properties of a polyisobutenyl succinimide. However, as
shown in FIG. 1 on page 76 of their article, the results of the
tests Forbes and Neustadter conducted indicate that succinimides
having a 1300 Mn polyisobutenyl substituent are more effective as
detergents than those having a polyisobutenyl substituent with a Mn
of 2000 or greater. In showing the effect of polyisobutenyl
molecular weight on succinimide detergency, this article teaches
that maximum detergency performance is obtained when the
polyisobutenyl group has a Mn of about 1300.
A recent article by S. T. Roby, R. E. Kornbrekke, and J. A. Supp
"Deposit Formulation in Gasoline Engines, Part 2, Dispersant
Effects on Sequence VE Deposits" JOURNAL OF THE SOCIETY OF
TRIBOLOGISTS AND LUBRICATION ENGINEERS, Vol. 50, 12, 989-995
(December 1994) teaches that the length of the dispersant alkyl
side chain influences deposit control performance, and that, at the
same nitrogen level, the low molecular weight (side chain 1000
daltons) dispersants that were tested were poorer than the tested
high molecular weight (side chain 2000 daltons) succinimide
dispersants. This teaching is also consistent with our prior
observation comparing 950 Mn side chain succinimides with 2200 Mn
side chain succinimides.
U.S. Pat. No. 4,234,435 teaches a preferred polyalkene-derived
substituent group with a Mn in the range of 1500-3200. For
polybutenes, an especially preferred Mn range is 1700-2400. This
patent also teaches that the succinimides must have a succinic
ratio of at least 1.3. That is, there should be at least 1.3
succinic groups per equivalent weight of polyalkene-derived
substituent group. Most preferably, the succinic ratio should be
from 1.5 to 2.5. This patent further teaches that its dispersants
also provide an improvement in viscosity index. That is, these
additives impart fluidity modifying properties to lubricant
compositions containing them. This is considered desirable for use
in multigrade lubricating oils but undesirable for single-grade
lubricating oils.
Polyamino alkenyl or alkyl succinimides and other additives useful
as dispersants and/or detergents, such as Mannich bases, contain
basic nitrogen. While basicity is an important property to have in
the dispersant/detergent additive, it is believed that the initial
attack on fluorocarbon elastomer seals used in some engines
involves attack by the basic nitrogen. This attack leads to the
loss of fluoride ions, and eventually results in cracks in the
seals and loss of other desirable physical properties in the
elastomer.
A variety of post-treatments for improving various properties of
alkenyl succinimides are known to the art, a number of which are
described in U.S. Pat. No. 5,241,003.
Example 2 of U.S. Pat. No. 5,266,186 discloses the preparation of
dispersants by reacting certain polyisobutenyl-succinic anhydride
adducts (see footnote 2 of Table 2) with ethylenediamine, followed
by reaction with a maleic anhydride/.alpha.-olefin copolymer. The
patent teaches that, by functioning as an iron sulfide dispersant,
the product is useful to inhibit sludge deposits in refinery
processing equipment caused by the heat treatment of hydrocarbon
feed stocks.
U.S. Pat. No. 5,112,507 discloses a polymeric ladder type polymeric
succinimide dispersant in which each side of the ladder is a long
chain alkyl or alkenyl, generally having at least about 30 carbon
atoms, preferably at least about 50 carbon atoms. The dispersant is
described as having improved hydrolytic stability and shear stress
stability, produced by the reaction of certain maleic
anhydride-olefin copolymers with certain polyamines. The patent
further teaches that the polymer may be post-treated with a variety
of post-treatments, and describes procedures for post-treating the
polymer with cyclic carbonates, linear mono- or polycarbonates;
boron compounds (e.g., boric acid), and fluorophosphoric acid and
ammonia salts thereof.
U.S. Pat. Nos. 5,334,321 and 5,356,552 disclose certain cyclic
carbonate post-treated alkenyl or alkylsuccinimides having improved
fluorocarbon elastomer compatibility, which are preferably prepared
by the reaction of the corresponding substituted succinic anhydride
with a polyamine having at least four nitrogen atoms per mole.
European Application, EP 0 682 102 A2 discloses a process which
comprises reacting: a copolymer of an olefin and maleic anhydride,
an acyclic hydrocarbyl-substituted succinic acylating agent, and an
alkylene polyamine. These products are useful in lubricating oil
compositions as additives for use as dispersants having viscosity
index improver properties.
SUMMARY OF THE INVENTION
The present invention provides novel polymers comprising
polyalkylene succinimides and post-treated derivatives thereof.
These polymers, and in particular the post-treated derivatives,
have excellent dispersant properties, improved hydrolytic and shear
stress stability, and improved fluorocarbon elastomer
compatibility. In a preferred embodiment the polymers are
essentially chlorine-free.
The polyalkylene succinimides of the present invention can be
prepared by the reaction of alkyl or alkenyl succinic acid
derivatives with certain copolymers of an unsaturated acidic
reagent (for example copolymers of unsaturated acidic reagents and
.alpha.-olefins) and a polyamine having at least three nitrogens
per molecule. The .alpha.-olefin moiety of the copolymer may also
be substituted with various substituents, so long as the
substituent does not interfere with the reaction or adversely
affect performance of the product. Because of competing and
sequential reactions, the reaction product will be a mixture of
compounds, which function as dispersants. Thus, by varying the mole
ratio of reactants, variations in the products, and correspondingly
variations in the properties of product, can be obtained. The
reaction product will be a mixture because all of the reactants are
generally furnished commercially as mixtures.
It is believed that the improvement in properties is primarily due
to the production of a new polyalkylene succinimide that can be
represented by the following formula: ##STR1##
wherein:
W is a nitrogen-containing group selected from the group consisting
##STR2##
R is a polyalkyl or polyalkylene having a number average molecular
weight of at least 1000 preferably from 1800 to 3000,
R.sup.1 is an alkyl having an average of from 12 to 28 carbon
atoms;
Z is a polyalkylene polyamine linking radical;
m is a whole integer of from 1 to 3
n is a whole integer of from 1 to 3;
x is a whole integer of from 2 to 20;
Int. is an initiating radical;
Ter. is a terminating group; and
wherein R.sup.2 and R.sup.3 are independently hydrogen, alkyl,
phenyl, or taken together are alkylene to give a ring group.
The (Int.) and (Ter.) substituent are carried over into the present
composition from the maleic anhydride reactant and are present in
the copolymer reactants as a result of the free radical initiator
used to prepare the copolymer. Typical (Int.) and (Ter.) group
include ##STR3##
wherein R.sup.5 is hydrogen, alkyl, aryl, alkaryl, cycloalkyl,
alkoxy, cycloalkoxy, acyl, alkenyl, cycloalkenyl, alkynyl; or
alkyl, aryl or alkaryl optionally substituted with 1 to 4
substituents independently selected from nitrile, keto, halogen,
nitro, alkyl, aryl, and the like; and R.sup.6 and R.sup.7 are
independently hydrogen, alkyl, aryl, alkaryl, and the like.
Typically the (Int.) group and (Ter.) group will be the same but
may also be different because of secondary or competing reactions
in the initial copolymerization or the subsequent reaction used to
prepare the composition of the present invention; including, in
some reaction with organic solvents such as toluene, resulting in a
benzyl radical initiator or terminating group.
The corresponding post-treated derivative can be obtained by
treating the reaction product with the desired post-treatment. For
example, the reaction product is preferably treated with a cyclic
carbonate, preferably ethylene carbonate, preferably by the
procedure described in U.S. Pat. Nos. 4,612,132 and 5,334,321
hereby incorporated by reference.
The present invention further provides lubricating oil compositions
comprising a major amount of a base oil of lubricating viscosity
and a minor amount of the compounds of the invention ("active
ingredients"). The active ingredients can be applied at effective
amounts, which are highly effective to control engine sludge and
varnish and yet be compatible with fluorocarbon elastomer engine
seals. The invention also provides a concentrate comprising about
20 to 60 wt. % of the compounds or compound mixtures and about 40
to 80 wt. % of a compatible liquid diluent designed to be added
directly to a base oil. Both the lubricating oil composition and
concentrate may also contain other additives designed to improve
the properties of the base oil, including other
detergent-dispersants.
The present invention further provides a fuel composition
comprising a major amount of hydrocarbons boiling in the gasoline
or diesel range and from 10 to 10,000 parts per million parts of
the hydrocarbon of a compound or mixture of compounds of the
present invention.
The composition of the present invention can be prepared reacting a
mixture under reactive conditions, wherein the mixture
comprises:
(a) an alkenyl or alkylsuccinic acid derivative, wherein the
alkenyl or alkyl substituent has a Mn of from 1800 to 3000;
(b) an unsaturated acidic reagent copolymer of
(1) an unsaturated acidic reagent and
(2) an olefin having an average of from 14 to 30 carbon atoms,
wherein the copolymer has a Mn of from 2000 to 4800; and
(c) a polyamine having at least three nitrogen atoms and 4 to 20
carbon atoms.
The mixture contains about from 1.5 to 10 equivalents of the
alkenyl or alkylsuccinic acid derivative per equivalent of the
unsaturated acidic reagent copolymer and about from 0.4 to 1.0
moles of the polyamine per equivalent of alkenyl or alkylsuccinic
acid derivative plus unsaturated acidic reagent copolymer.
Preferably, the acid derivative is an anhydride, and the
unsaturated acidic reagent copolymer is a copolymer of maleic
anhydride and an olefin, and the polyamine has at least six
nitrogen atoms per mole.
Additional aspects of the invention will be apparent from the
following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect, the present invention involves a polymer
having the general formula: ##STR4##
wherein:
W is a nitrogen-containing group selected from the group consisting
##STR5##
R is a polyalkyl or polyalkylene having a number average molecular
weight of from 1800 to 3000,
R.sup.1 is an alkyl having an average of from 12 to 28 carbon
atoms;
Z is a polyalkylene polyamine linking radical;
m is a whole integer of from 1 to 3
n is a whole integer of from 1 to 3;
x is a whole integer of from 2 to 20;
Int. is an initiating radical;
Ter. is a terminating group; and
wherein R.sup.2 and R.sup.3 are independently hydrogen, alkyl,
phenyl, or taken together are alkylene to give a ring group.
In simplified terms, the compound of formula (I), shown above, can
be considered a polyalkylene succinimide produced by the reaction
of a copolymer (the unsaturated acidic reagent copolymer) with a
monomer (the alkene or alkyl succinic acid derivative) in which the
monomer is linked to the polymer units by a polyamine linking
group. Because the polyalkylene succinimide mixture contains about
from 1.5 to 10 equivalents of alkenyl or alkylsuccinic acid
derivative per equivalent of unsaturated acidic reagent copolymer,
and about from 0.4 to 1.0 equivalents of polyamine per equivalent
of alklenyl or alkylsuccinic acid derivative plus unsaturated
acidic reagent copolymer, other structures, such as (II) and (III),
shown below, can also be present, depending on the ratios of
alkenyl or alkylsuccinic acid derivative, unsaturated acidic
reagent copolymer, and polyamine. ##STR6##
wherein W, R, R.sup.1, R.sup.2, and R.sup.3, Z, m, n, x, Int., Ter
are the same as described above.
In addition to the predominant polymer of formula (I), (II), or
(III), the reaction will typically contain more complex reaction
products and polymers because of competing and sequential
reactions, and because the alkenyl or alkylsuccinic acid derivative
might contain more than one succinic anhydride moiety per long
chain alkyl or alkenyl group or contain unsaturated acidic reagent
oligomers.
Referring to formulas (I), (II), and (III), the preferred compounds
or compound mixtures are those wherein Z is a polyamino radical
having about from 3 to 7, more preferably, about 4 to 5 nitrogen
atoms and 8 to 20 carbon atoms.
The initiating group and terminating group will be a function of
the initiator used to initiate the free radical reaction used to
prepare the copolymer and may vary with the particular copolymer
and secondary reactions. Discounting secondary reactions, the
preferred Int. and Ter. groups are where R.sup.1 is a preferred
alkyl group are ##STR7##
Definitions
As used herein the following terms have the following meanings,
unless expressly stated to the contrary.
The term "succinimide" is understood in the art to include many of
the amide, imide, etc. species which are also formed by the
reaction of a succinic anhydride with an amine. The predominant
product, however, is succinimide and this term has been generally
accepted as meaning the product of a reaction of an alkenyl- or
alkyl-substituted succinic acid or anhydride with a polyamine.
Alkenyl or alkyl succinimides are disclosed in numerous references
and are well known in the art. Certain fundamental types of
succinimides and related materials encompassed by the term of art
"succinimide" are taught in U.S. Pat. Nos. 2,992,708; 3,018,291;
3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746, the
disclosures of which are hereby incorporated by reference.
The term "Total Base Number" or "TBN" refers to the amount of base
equivalent to milligrams of KOH in 1 gram of sample. Thus, higher
TBN numbers reflect more alkaline products and therefore a greater
alkalinity reserve. The TBN of a sample can be determined by ASTM
Test No. D2896 or any other equivalent procedure.
The term "SAP" refers to Saponification Number and can be
determined by the procedure described in ASTM D94 or any other
equivalent procedure.
The term "TAN" refers to Total Acid Number and can be determined by
the procedure described in ASTM D 664 or any other equivalent
procedure.
The "succinic ratio" or "succination ratio" refers to the ratio
calculated in accordance with the procedure and mathematical
equation set forth in columns 5 and 6 of U.S. Pat. No. 5,334,321,
hereby incorporated by reference. The calculation is asserted to
represent the average number of succinic groups in an alkenyl or
alkylsuccinic anhydride per alkenyl or alkyl chain.
The term "PIBSA" means polyisobutenyl succinic anhydride.
The term "hydrocarbon soluble compatible salt" refers to a salt
which is soluble in an oil of lubricating viscosity or a
hydrocarbon fuel suitable for use in spark-ignition or diesel
engines and which is compatible with such composition.
The term "alkenyl or alkylsuccinic acid derivative" refers to a
structure having the formula ##STR8##
wherein L and M are independently selected from the group
consisting of --OH, --Cl, --O--, lower alkyl or taken together are
--O-- to form an alkenyl or alkylsuccinic anhydride group.
The term "unsaturated acidic reagent" refers to maleic or fumaric
reactants of the general formula: ##STR9##
wherein X and X' are the same or different, provided that at least
one of X and X' is a group that is capable of reacting to esterify
alcohols, form amides, or amine salts with ammonia or amines, form
metal salts with reactive metals or basically reacting metal
compounds and otherwise function as acylating agents. Typically, X
and/or X' is --OH, --O-hydrocarbyl, --OM.sup.+ where M.sup.+
represents one equivalent of a metal, ammonium or amine cation,
--NH.sub.2, --Cl, --Br, and taken together X and X' can be --O-- so
as to form an anhydride. Preferably, X and X' are such that both
carboxylic functions can enter into acylation reactions. Maleic
anhydride is a preferred unsaturated acidic reactant. Other
suitable unsaturated acidic reactants include electron-deficient
olefins such as monophenyl maleic anhydride; monomethyl, dimethyl,
monochloro, monobromo, monofluoro, dichloro and difluoro maleic
anhydride, N-phenyl maleimide and other substituted maleimides;
isomaleimides; fumaric acid, maleic acid, alkyl hydrogen maleates
and fumarates, dialkyl fumarates and maleates, fumaronilic acids
and maleanic acids; and maleonitrile, and fumaronitrile.
Synthesis
The compounds of the present invention can be prepared by
contacting the desired alkyl or alkenyl succinic acid derivative
with an unsaturated acidic reagent copolymer and polyamine under
reactive conditions: ##STR10##
wherein R, R.sup.1, Z, L, M, n, (Int) and (Ter) are as defined
above.
Typically the above process is conducted by contacting from 1.5 to
10 equivalents of alkenyl or alkylsuccinic acid derivative (A) per
mole of unsaturated acidic reagent copolymer (B) and from 0.4 to
1.0 equivalents of amine (C) per equivalent of alkenyl or
alkylsuccinic acid derivative (A) plus unsaturated acidic reagent
copolymer (B). In conducting this reaction we have generally found
it convenient to first add the alkenyl or alkylsuccinic acid
derivative and the unsaturated acidic reagent copolymer together
and then add the polyamine. It may be desirable to conduct the
reaction in an inert organic solvent. Optimum solvents will vary
with the particular copolymer and can be determined from literature
sources or routine experimentations. For example, in the case of
maleic anhydride poly .alpha.-olefin copolymers, we found that 100N
diluent oil and mixtures of C.sub.9 aromatic solvents are
acceptable solvents.
We have found that when less than 1.5 equivalents of alkenyl or
alkylsuccinic acid derivative (A) per mole of unsaturated acidic
reagent copolymer (B) are used then the polymer sometimes contains
gels, which is undesirable.
Typically, the reaction is conducted at temperatures in the range
of about from 140 to 180.degree. C., preferably 150 to 170.degree.
C. for about from 1 to 10 hours, preferably 4 to 6 hours. Typically
the reaction is conducted at about atmospheric pressure; however,
higher or lower pressures can also be used depending on the
reaction temperature desired and the boiling point of the reactants
or solvent.
As above noted, the reaction product will typically be a mixture,
both because of the secondary products or byproducts and also
because the reactants will typically be mixtures. In theory, pure
compounds could be obtained, for example by using pure compounds as
reactants and then separating out the desired pure compounds from
the reaction product. However, commercially, the expense of this
would rarely be justified and accordingly the commercial product
will generally be a mixture in which formulas (I), (II), and (III)
will be the predominant compounds.
Water, present in the system or generated by the reaction of the
amine with the succinic or maleic anhydride moieties of (A) and (B)
alkyl succinimide, is preferably removed from the reaction system
during the course of the reaction via azeotroping or distillation.
After reaction completion, the system can be stripped at elevated
temperatures (typically 100.degree..quadrature. C. to
250.degree..quadrature. C.) and reduced pressures to remove any
volatile components which may be present in the product.
The Alkenyl or AlkylSuccinic Acid Derivatives--Reactant (A)
Alkyl and alkenylsuccinic acid derivatives having a calculated
succinic ratio of about from 1:1 to 2.5:1, and preferably about
from 1:1 to 1.5:1, may be used in the present process. More
preferably, the alkyl or alkenyl succinic acid derivatives have a
succination ratio of about from 1:1 to 1.2:1. Most preferably,
alkyl or alkenylsuccinic anhydrides are used. Accordingly we prefer
to use alkenyl succinic anhydride prepared by the thermal process,
both because the calculated succination ratio of material prepared
by this process is typically 1.0 to 1.2, and because the produce is
essentially chlorine-free because chlorine is not used in the
synthesis.
The thermal reaction of a polyolefin with maleic anhydride is well
known and is described, for example, in U.S. Pat. No. 3,361,673.
The less desirable is the chlorination process characterized by the
reaction of a chlorinated polyolefin, with maleic anhydride, which
is also well known and is described, for example, in U.S. Pat. No.
3,172,189. Various modifications of the thermal process and
chlorination process are also well known, some of which are
described in U.S. Pat. Nos. 4,388,471; 4,450,281; 3,018,250 and
3,024,195. Free radical procedures for preparing alkenyl succinic
anhydrides are, for example, described in U.S. Pat. Nos. 5,286,799
and 5,319,030. All of the above referenced patents are hereby
incorporated herein by reference in their entirety.
In accordance with the invention, the alkenyl or alkyl succinic
anhydride reactant is derived from a polyolefin having a Mn from
1000 to 5000 and a Mw/Mn ratio of 1:1 to 5:1. In a preferred
embodiment, the alkenyl or alkyl group of the succinimide has a Mn
value from 1800 to 3000. Most preferred are alkenyl or alkyl
substituents having a Mn of from 2000 to 2500.
Suitable polyolefin polymers for reaction with maleic anhydride
include polymers comprising a major amount of C.sub.2 to C.sub.5
monoolefin, e.g., ethylene, propylene, butylene, iso-butylene and
pentene. The polymers can be homopolymers, such as polyisobutylene,
as well as copolymers of two or more such olefins, such as
copolymers of: ethylene and propylene, butylene, and isobutylene,
etc. Other copolymers include those in which a minor amount of the
copolymer monomers (e.g., 1 to 20 mole percent), is a C.sub.4 to
C.sub.8 nonconjugated diolefin, e.g., a copolymer of isobutylene
and butadiene or a copolymer of ethylene, propylene and
1,4-hexadiene, etc.
A particularly preferred class of olefin polymers for reaction with
maleic anhydride comprises the polybutenes, which are prepared by
polymerization of one or more of 1-butene, 2-butene and isobutene.
Especially desirable are polybutenes containing a substantial
proportion of units derived from isobutene. The polybutene may
contain minor amounts of butadiene, which may or may not be
incorporated in the polymer. These polybutenes are readily
available commercial materials well known to those skilled in the
art. Examples of procedures illustrating the preparation of such
material can be found, for example, in U.S. Pat. Nos. 3,215,707;
3,231,587; 3,515,669; 3,579,450; 3,912,764 and 4,605,808, hereby
incorporated by reference for their disclosures of suitable
polybutenes.
The alkenyl or alkylsuccinic anhydride may also be prepared using
the so-called highly reactive or high methyl vinylidene
polyalkylene, most commonly polyisobutene, such as described in
U.S. Pat. Nos. 4,152,499; 5,071,919; 5,137,980; 5,286,823;
5,254,649; published International Applications Numbers WO 93
24539-A1; WO 9310063-A1; and published European Patent Applications
Numbers 0355895-A; 0565285A; and 0587381A, all of which are hereby
incorporated by reference in their entirety. Other polyalkenes can
also be used including, for example, polyalkenes prepared using
metallocene catalysts such as for example described in published
German patent application DE 4313088A1.
The Unsaturated Acidic Reagent Copolymer--Reactant (B)
The unsaturated acidic reagent copolymers used in the present
invention can be random copolymers or alternating copolymers, and
can be prepared by known procedures. Further, in most instances,
examples of each class are readily commercially available. Such
copolymers may be prepared by the free radical reaction of an
unsaturated acidic reagent with the corresponding monomer of the
other unit of the copolymer. Thus, in the present case, the monomer
will correspond to R.sup.1 in formula (I) plus a vinyl group, i.e.,
R.sup.1 --CH=CH.sub.2. Hence, where R.sup.1 is phenyl the monomer
will be styrene. Accordingly, the unsaturated acidic reagent
copolymer can be prepared by the free radical reaction of an
unsaturated acidic reagent, preferably maleic anhydride, with the
corresponding C.sub.8 to C.sub.48 .alpha.-olefin, C.sub.8 to
C.sub.28 polyalkylene, ethylene, styrene, 1,3-butadiene, C.sub.3+
vinyl alkyl ether, or C.sub.4+ vinyl alkanoate.
We prefer to use alpha olefins from C.sub.12 to C.sub.28 because
these materials are commercially readily available, and because
they offer a desirable balance of the length of the molecular
weight tail, and the solubility of the copolymer in non polar
solvents. Mixtures of olefins, eg C.sub.14, C.sub.16, and C.sub.18
are especially desirable.
The degree of polymerization of the copolymers can vary over a wide
range. In general copolymers of high molecular weight can be
produced at low temperatures and copolymers of low molecular weight
can be produced at high temperatures. It has been generally shown
that for the polymers of this invention, we prefer low molecular
weight copolymers, i.e., low molecular weight (2000-5500 for
example) because higher molecular weight copolymers (greater than
10,000 for example) can sometimes produce polymers that contain
gels.
The copolymerization is conducted in the presence of a suitable
free radical initiator; typically a peroxide type initiator, e.g.
di(t-butyl) peroxide dicumyl peroxide or azo type initiator, e.g.,
isobutylnitrile type initiators. Procedures for preparing poly
.alpha.-olefin copolymers are, for example, described in U.S. Pat.
Nos. 3,560,455 and 4,240,916, hereby incorporated by reference in
their entirety. Both patents also describe a variety of
initiators.
Some examples of maleic anhydride .alpha.-olefin copolymers
are:
Poly(styrene-co-maleic anhydride) resins: These materials are known
as SMA.RTM. resins. There are two molecular weight versions. The
low molecular weight resin is called SMA resin and is available
from ARCO Chemical with styrene to maleic anhydride ratio's of 1:1,
2:1, and 3:1. The high molecular weight resin is produced by
Monsanto (Lytron.RTM.), ARCO (Dylark.RTM.) or American Cyanamide
(Cypress.RTM.). Other names for SMA copolymers are Styrolmol, Maron
MS, and Provimal ST resins. In some cases partially esterified
resins are also available.
Poly(ethylene-co-maleic anhydride) resins: These materials are
manufactured by Monsanto under the trade name EMA.RTM.. They are
also called Malethamer and Vinac resins.
Poly(alpha olefin-co-maleic anhydride) resins are available from
Chevron Chemical as PA-18 (octadecene-1-co-maleic anhydride), or
can be prepared as in Preparation 1. Alternately mixtures of alpha
olefins can be used. These materials have been described in U.S.
Pat. Nos. 3,461,108; 3,560,455; 3,560,456; 3,560,457; 3,580,893;
3,706,704; 3,729,450; and 3,729,451. Partially esterified olefin co
maleic anhydride resins can also be used. Some examples of these
types of resins are called Ketjenlube.RTM. resins available from
AKZO Co.
Poly(isobutene-co-maleic anhydride) resins are called ISOBAM.RTM.
and are manufactured by Curaray Co. Ltd. They are also available
from Humphrey chemical Co. under the code K-66.
Poly(butadiene-so-maleic anhydride) resins are called Maldene.RTM.
and are made by Borg-Warner Corp.
Poly(methylvinylether-co-maleic anhydride) resins are sold by GAF
Corporation under the name Gantrey An. Other names are called Visco
Frey.
Poly(vinylacetate-co-maleic anhydride) resins are available from
Monsanto and are called Lytron 897, 898, and 899. They are also
called Pouimalya resins in Europe.
We have found that excellent results can be obtained using a
copolymer prepared by the free radical polymerization of maleic
anhydride and C.sub.12 to C.sub.18 .alpha.-olefins or olefin
mixtures thereof.
The Polyamine Reactant (C)
The polyamine reactant should have at least three amine nitrogen
atoms per mole, and preferably 4 to 12 amine nitrogens per
molecule. Most preferred are polyamines having from about 6 to
about 10 nitrogen atoms per molecule. The number of amine nitrogen
atoms per molecule of polyamine is calculated as follows:
##EQU1##
wherein
% N=percent nitrogen in polyamine or polyamine mixture
M.sub.pa =number average molecular weight of the polyamine or
polyamine mixture
Preferred polyalkylene polyamines also contain from about 4 to
about 20 carbon atoms, there being preferably from 2 to 3 carbon
atoms per alkylene unit. The polyamine preferably has a
carbon-to-nitrogen ratio of from 1:1 to 10:1.
Examples of suitable polyamines that can be used to form the
compounds of this invention include the following: tetraethylene
pentamine, pentaethylene hexamine, Dow E-100.RTM. heavy polyamine
(number average M.sub.w =303, available from Dow Chemical Company,
Midland, Mich.), and Union Carbide HPA-X heavy polyamine (number
average M.sub.w =275, available from Union Carbide Corporation,
Danbury, Conn.). Such amines encompass isomers, such as
branched-chain polyamines, and the previously mentioned substituted
polyamines, including hydrocarbyl-substituted polyamines. HPA-X
heavy polyamine ("HPA-X") contains an average of approximately 6.5
amine nitrogen atoms per molecule. Such heavy polyamines generally
afford excellent results.
The polyamine reactant may be a single compound but typically will
be a mixture of compounds reflecting commercial polyamines.
Typically the commercial polyamine will be a mixture in which one
or several compounds predominate with the average composition
indicated. For example, tetraethylene pentamine prepared by the
polymerization of aziridine or the reaction of dichloroethylene and
ammonia will have both lower and higher amine members, e.g.,
triethylene tetramine ("TETA"), substituted piperazines and
pentaethylene hexamine, but the composition will be largely
tetraethylene pentamine and the empirical formula of the total
amine composition will closely approximate that of tetraethylene
pentamine.
Other examples of suitable polyamines include admixtures of amines
of various sizes, provided that the overall mixture contains at
least 4 nitrogen atoms per molecule. Included within these suitable
polyamines are mixtures of diethylene triamine ("DETA") and heavy
polyamine. A preferred polyamine admixture reactant is a mixture
containing 20% by weight DETA and 80% by weight HPA-X; as
determined by the method described above, this preferred polyamine
reactant contains an average of about 5.2 nitrogen atoms per
mole.
Methods of preparation of polyamines and their reactions are
detailed in Sidgewick's THE ORGANIC CHEMISTRY OF NITROGEN,
Clarendon Press, Oxford, 1966; Noller's CHEMISTRY OF ORGANIC
COMPOUNDS, Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-Othmer's
ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 2nd Ed., especially Volumes 2,
pp. 99-116.
Post-Treatments
We have found that the dispersancy of the present polymers is
generally further improved by reaction with a cyclic carbonate.
This may result in some reduction in fluorocarbon elastomer
compatibility. However, this generally can be most than offset by
reducing the concentration of the carbonated post-treated polymer
in light of the increased dispersancy. The cyclic carbonate
post-treatment is especially advantageous where the dispersant will
be used in engines which do not have fluorocarbon elastomer seals.
The resulting modified polymer has one or more nitrogens of the
polyamino moiety substituted with a hydroxy hydrocarbyl
oxycarbonyl, a hydroxy poly(oxyalkylene)oxycarbonyl, a
hydroxyalkylene, hydroxyalkylenepoly-(oxyalkylene), or mixture
thereof.
The cyclic carbonate post-treatment is conducted under conditions
sufficient to cause reaction of the cyclic carbonate with secondary
amino group of the polyamino substituents. Typically, the reaction
is conducted at temperatures of about from 0.degree. C. to
250.degree. C. preferably about from 100.degree. C. to 200.degree.
C. Generally, best results are obtained at temperatures of about
from 150.degree. C. to 180.degree. C.
The reaction may be conducted neat, wherein both the polymer and
the cyclic carbonate are combined in the proper ratio, either alone
or in the presence of a catalyst (such as an acidic, basic or Lewis
acid catalyst). Depending on the viscosity of the polymer reactant,
it may be desirable to conduct the reaction using an inert organic
solvent or diluent, for example, toluene, xylene. Examples of
suitable catalysts include, for example, phosphoric acid, boron
trifluoride, alkyl or aryl sulfonic acid, alkali or alkaline
carbonate. Generally, the same solvents or diluents as described
above with respect to the preparation for the co-polymer (A) or
polymer (I) can also be used in the cyclic carbonate
post-treatment.
The reaction of polyamino alkenyl or alkyl succinimides with cyclic
carbonates is known in the art and is described in U.S. Pat. No.
4,612,132, hereby incorporated by reference, in its entirety.
Generally, the procedures described to post-treat polyamino alkenyl
or alkyl succinimides with cyclic carbonates can also be applied to
post-treat the present polymers.
A particularly preferred cyclic carbonate is 1,3-dioxolan-2-one
(ethylene carbonate) because it affords excellent results and also
because it is readily commercially available.
The molar charge of cyclic carbonate employed in the post-treatment
reaction is preferably based upon the theoretical number of basic
nitrogens contained in the polyamino substituent of the
succinimide. Thus, when one equivalent of tetraethylene pentamine
("TEPA") is reacted with one equivalent of succinic anhydride and
one equivalent of copolymer, the resulting bis succinimide will
theoretically contain 3 basic nitrogens. Accordingly, a molar
charge of 2 would require that two moles of cyclic carbonate be
added for each basic nitrogen or in this case 6 moles of cyclic
carbonate for each mole equivalent of polyalkylene succinimide or
succinimide prepared from TEPA. Mole ratios of the cyclic carbonate
to the basic amine nitrogen of the polyamino alkenyl succinimide
employed in the process of this invention are typically in the
range of from about 1:1 to about 4:1; although preferably from
about 2:1 to about 3:1.
As described in U.S. Pat. No. 4,612,132, cyclic carbonates may
react with the primary and secondary amines of a polyamino alkenyl
or alkyl succinimide to form two types of compounds. In the first
instance, strong bases, including unhindered amines such as primary
amines and some secondary amines, react with an equivalent of
cyclic carbonate to produce a carbamic ester. In the second
instance, hindered bases, such as hindered secondary amines, may
react with an equivalent of the same cyclic carbonate to form a
hydroxyalkyleneamine linkage. (Unlike the carbamate products, the
hydroxyalkyleneamine products retain their basicity.) Accordingly,
the reaction of a cyclic carbonate may yield a mixture of products.
When the molar charge of the cyclic carbonate to the basic nitrogen
of the succinimide is about 1 or less, a large portion of the
primary and secondary amines of the succinimide will be converted
to hydroxy hydrocarbyl carbamic esters with some
hydroxyhydrocarbylamine derivatives also being formed. As the mole
ratio is raised above 1 increased amounts of poly(oxyalkylene)
polymers of the carbamic esters and the hydroxyhydrocarbylamine
derivatives are produced.
Both the polymers and post-treated polymers of this invention can
also be reacted with boric acid or a similar boron compound to form
borated dispersants having utility within the scope of this
invention. In addition to boric acid (boron acid), examples of
suitable boron compounds include boron oxides, boron halides and
esters of boric acid. Generally from about 0.1 equivalents to 10
equivalents of boron compound to the modified succinimide may be
employed.
In addition to the carbonate and boric acids post-treatments both
the compounds may be post-treated, or further post-treatment, with
a variety of post-treatments designed to improve or impart
different properties. Such post-treatments include those summarized
in columns 27-29 of U.S. Pat. No. 5,241,003, hereby incorporated by
reference. Such treatments include, treatment with:
Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat. Nos.
3,403,102 and 4,648,980);
Organic phosphorous compounds (e.g., U.S. Pat. No. 3,502,677);
Phosphorous pentasulfides;
Boron compounds as already noted above (e.g., U.S. Pat. Nos.
3,178,663 and 4,652,387);
Carboxylic acid, polycarboxylic acids, anhydrides and/or acid
halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,386);
Epoxides polyepoxiates or thioexpoxides (e.g., U.S. Pat. Nos.
3,859,318 and 5,026,495);
Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530);
Carbon disulfide (e.g., U.S. Pat. No. 3,256,185);
Glycidol (e.g., U.S. Pat. No. 4,617,137);
Urea, thourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619;
3,865,813; and British Patent GB 1,065,595);
Organic sulfonic acid (e.g., U.S. Pat. No. 3,189,544 and British
Patent GB 2,140,811);
Alkenyl cyanide (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569);
Diketene (e.g., U.S. Pat. No. 3,546,243);
A diisocyanate (e.g., U.S. Pat. No. 3,573,205);
Alkane sultone (e.g., U.S. Pat. No. 3,749,695);
1,3-Dicarbonyl Compound (e.g., U.S. Pat. No. 4,579,675);
Sulfate of alkoxylated alcohol or phenol (e.g., U.S. Pat. No.
3,954,639);
Cyclic lactone (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515;
4,668,246; 4,963,275; and 4,971,711);
Cyclic carbonate or thiocarbonate linear monocarbonate or
polycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132;
4,647,390; 4,648,886; 4,670,170);
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. 4,971,598 and
British Patent GB 2,140,81 1);
Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No.
4,614,522);
Lactam, thiolactam, thiolactone or ditholactone (e.g., U.S. Pat.
Nos. 4,614,603 and 4,666,460);
Cyclic carbonate or thiocarbonate, linear monocarbonate or
plycarbonate, or chloroformate (e.g., U.S. Pat. Nos. 4,612,132;
4,647,390; 4,646,860; and 4,670,170);
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. No. 4,971,598
and British Patent GB 2,440,811);
Hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. No.
4,614,522);
Lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S. Pat.
Nos. 4,614,603, and 4,666,460);
Cyclic carbamate, cyclic thiocarbamate or cyclic dithiocarbamate
(e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459);
Hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. Nos. 4,482,464;
4,521,318; 4,713,189);
Oxidizing agent (e.g., U.S. Pat. No. 4,379,064);
Combination of phosphorus pentasulfide and a polyalkylene polyamine
(e.g., U.S. Pat. No. 3,185,647);
Combination of carboxylic acid or an aldehyde or ketone and sulfur
or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086; 3,470,098);
Combination of a hydrazine and carbon disulfide (e.g. U.S. Pat. No.
3,519,564);
Combination of an aldehyde and a phenol (e.g., U.S. Pat. Nos.
3,649,229; 5,030,249; 5,039,307);
Combination of an aldehyde and an O-diester of dithiophosphoric
acid (e.g., U.S. Pat. No. 3,865,740);
Combination of a hydroxyaliphatic carboxylic acid and a boric acid
(e.g., U.S. Pat. No. 4,554,086);
Combination of a hydroxyaliphatic carboxylic acid, then
formaldehyde and a phenol (e.g., U.S. Pat. No. 4,636,322);
Combination of a hydroxyaliphatic carboxylic acid and then an
aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064);
Combination of formaldehyde and a phenol and then glycolic acid
(e.g., U.S. Pat. No. 4,699,724);
Combination of a hydroxyaliphatic carboxylic acid or oxalic acid
and then a diisocyanate (e.g. U.S. Pat. No. 4,713,191);
Combination of inorganic acid or anhydride of phosphorus or a
partial or total sulfur analog thereof and a boron compound (e.g.,
U.S. Pat. No. 4,857,214);
Combination of an organic diacid then an unsaturated fatty acid and
then a nitrosoaromatic amine optionally followed by a boron
compound and then a glycolating agent (e.g., U.S. Pat. No.
4,973,412);
Combination of an aldehyde and a triazole (e.g., U.S. Pat. No.
4,963,278);
Combination of an aldehyde and a triazole then a boron compound
(e.g., U.S. Pat. No. 4,981,492);
Combination of cyclic lactone and a boron compound (e.g., U.S. Pat.
Nos. 4,963,275 and 4,971,711).
Lubricating Oil Compositions and Concentrates
The compositions of this invention are compatible with fluorocarbon
elastomer seals, at concentrations at which they are effective as
detergent and dispersant additives in lubricating oils. When
employed in this manner, the modified polyamino alkenyl or alkyl
succinimide additive is usually present in from 1 to 5 percent by
weight (on a dry polymer basis) to the total composition and
preferably less than 3 percent by weight (on a dry or actives
polymer basis). Dry or actives basis indicates that only the active
ingredient of this invention are considered when determining the
amount of the additive relative to the remainder of a composition
(e.g., lube oil composition, lube oil concentrate, fuel composition
or fuel concentrate). Diluents and any other inactives are
excluded. Unless otherwise indicated, in describing the lubricating
oil and final compositions or concentrates, dry or active
ingredient contents are intended with respect to the polyalkylene
succinimides. This includes the novel polyalkylene succinimides of
the present invention and also other reaction product or byproducts
in the reaction product mixture which function as dispersants.
The lubricating oil used with the additive compositions of this
invention may be mineral oil or synthetic oils of lubricating
viscosity and preferably suitable for use in the crankcase of an
internal combustion engine. Crankcase lubricating oils typically
have a viscosity of about 1300 cSt at 0.degree. F. (-17.8.degree.
C.) to 22.7 cSt at 210.degree. F. (99.degree. C.). The lubricating
oils may be derived from synthetic or natural sources. Mineral oil
for use as the base oil in this invention includes paraffinic,
naphthenic and other oils that are ordinarily used in lubricating
oil compositions. Synthetic oils include both hydrocarbon synthetic
oils and synthetic esters. Useful synthetic hydrocarbon oils
include liquid polymers of alpha olefins having the proper
viscosity. Especially useful are the hydrogenated liquid oligomers
of C.sub.6 to C.sub.12 alpha olefins such as 1-decene trimer.
Likewise, alkyl benzenes of proper viscosity such as didodecyl
benzene can be used. Useful synthetic esters include the esters of
both monocarboxylic acid and polycarboxylic acids as well as
monohydroxy alkanols and polyols. Typical examples are didodecyl
adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate,
dilaurylsebacate and the like. Complex esters prepared from
mixtures of mono and dicarboxylic acid and mono and dihydroxy
alkanols can also be used.
Blends of hydrocarbon oils with synthetic oils are also useful. For
example, blends of 10 to 25 weight percent hydrogenated 1-decene
trimmer with 75 to 90 weight percent 150 SUS (100.degree. F.)
mineral oil gives an excellent lubricating oil base.
Other additives which may be present in the formulation include
detergents (overbased and non-overbased), rust inhibitors, foam
inhibitors, corrosion inhibitors, metal deactivators, pour point
depressants, antioxidants, wear inhibitors, zinc dithiophosphates
and a variety of other well-known additives.
It is also contemplated the modified succinimides of this invention
may be employed as dispersants and detergents in hydraulic fluids,
marine crankcase lubricants and the like. When so employed, the
modified succinimide is added at from 0.1 to 5 percent by weight
(on a dry polymer basis) to the oil, and preferably at from 0.5 to
5 weight percent (on a dry polymer basis).
Additive concentrates are also included within the scope of this
invention. The concentrates of this invention usually include from
90 to 10 weight percent of an organic liquid diluent and from 10 to
90 weight percent (on a dry polymer basis) of the additive of this
invention. Typically, the concentrates contain sufficient diluent
to make them easy to handle during shipping and storage. Suitable
diluents for the concentrates include any inert diluent, preferably
an oil of lubricating viscosity, so that the concentrate may be
readily mixed with lubricating oils to prepare lubricating oil
compositions. Suitable lubricating oils which can be used as
diluents typically have viscosities in the range from about 35 to
about 500 Saybolt Universal Seconds (SUS) at 100.degree. F.
(38.degree. C.), although an oil of lubricating viscosity may be
used.
Fuel Compositions and Concentrates
Typically the fuel composition will about from 10 to 10,000 weight
parts per million, preferably from 30 to 2,000 weight parts per
million, of base fuel. This is based on active ingredient including
the other dispersant reaction products as well as the compounds of
formula (I) but excluding inactives for example diluent oil and any
unreacted alkene or poly .alpha.-olefins etc. carried through from
the preparation of succinic anhydride (A) or copolymer (B). If
other detergents are present, a lesser amount of the modified
succinimide may be used. Optimum concentrations can vary with the
particular base oil and the presence of other additives, but, can
be determined by routine procedures.
The compositions of this invention may also be formulated as a fuel
concentrate, using an inert stable oleophilic organic solvent
boiling in the range of about 150.degree. F. to 400.degree. F.
Preferably, an aliphatic or an aromatic hydrocarbon solvent is
used, such as benzene, toluene, xylene or higher-boiling aromatics
or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon
atoms, such as isopropanol, isobutylcarbinol, n-butanol and the
like, in combination with hydrocarbon solvents are also suitable
for use with the fuel additive. The present fuel concentrate will
typically contain about from 20 to 60 wt. % of the present
composition or an active ingredient basis.
PREPARATIONS AND EXAMPLES
A further understanding of the invention can be had in the
following nonlimiting Preparations and Examples. Wherein unless
expressly stated to the contrary, all temperatures and temperature
ranges refer to the Centigrade system and the term "ambient" or
"room temperature" refers to about 20.degree. C.-25.degree. C. The
term "percent" or "%" refers to weight percent and the term "mole"
or "moles" refers to gram moles. The term "equivalent" refers to a
quantity of reagent equal in moles, to the moles of the preceding
or succeeding reactant recited in that example in terms of finite
moles or finite weight or volume.
Preparation 1
Maleic Anhydride --C.sub.14-18 Alpha Olefin Copolymer
Concentrate
This example illustrates a suitable procedure for preparing the
title compound. In this example 170 grams of a mixture of C.sub.14,
C.sub.16 and C.sub.18 Olefins and 50 g of C.sub.9 aromatic solvent
is heated to 300.degree. F. (149.degree. C.) then sparged with
nitrogen to remove entrained air and then cooled to 150.degree. F.
(66.degree. C.). 75 grams of maleic anhydride is added and the
temperature of the mixture raised to 255.degree. F. (124.degree.
C.). A total of 14 g of Di-t-butyl peroxide is added in five equal
portions at about 30-minute increments over a period of two hours.
During the additions the temperature is maintained between
255.degree. F. to 265.degree. F. and then allowed to slowly
increase to 300.degree. F. (149.degree. C.) and held at about this
temperature for two hours and then cooled affording a mixture of
the title composition and solvent. This is used without further
purification.
Preparation 2
Preparation of Pibsa 2200 (Succinic Ratio=1.1)
A 35.186 Kg, 16 mole, of a 2200 Mn polybutene sold under the
trademark Parapol 2200 by Exxon Chemical Company) is charged to a
reactor and heated to 232.degree. C. During this time, the reactor
is pressurized to 40 psig with nitrogen and then vented three times
to remove air. The reactor is repressurized to 24.7 psia and 1500 g
maleic anhydride then added over a thirty-minute period. Following
this, another 4581 g of maleic anhydride is added over a 4-hour
period. The total charge mole ratio (CMR) of maleic anhydride to
polybutene is 3.88. After the maleic anhydride addition is
completed, the reaction is held at 232.degree. C. for 1.5 hours and
then cooled. Any unreacted maleic anhydride is removed by vacuum
distillation at 0.4 psia a light neutral diluent oil is added to
the stripped product and heated to 160.degree. C. for 24 hours and
was then filtered. This product was found to contain 37.68 wt. %
actives and had a saponification number of 19.7 mg KOH/g sample.
The succinic ratio was 1.1 based on a polybutene molecular weight
of 2246 determined by gel permeation chromatography ("GPC").
Preparation 3
Preparation of Pibsa 1300 (Succinic Ratio=1.1)
The procedure of Preparation 2 is repeated except that a 1300 Mn
polybutene sold under the trademark Parapol 1300 by Exxon Chemical
Company is used instead of Parapol 2200.TM.. After dilution with
diluent oil and filtration, this product was found to contain 49.6
wt. % actives and a saponification number of 42.2 mg KOH/g sample.
The succinic ratio was 1.1 based on a polybutene molecular weight
of 1300.
Preparation 4
Preparation of Pibsa 2200 (Succinic Ratio=1.5)
Parapol 2200.TM., 42.8 Kg, 19.45 mol, is charged to a reactor and
the temperature increased to 150.degree. C. During this time, the
reactor is pressurized to 40 psig with nitrogen and then vented
three times to remove oxygen. Then at 150.degree. C., maleic
anhydride, 4294 g, 43.82 mol, and di-t-butylperoxide, 523 g, 3.58
mol, is added. The first 25% is added over 30 minutes. The
remainder is then added over 11.5 hours. The CMR of maleic
anhydride to polybutene is 2.25. The mixture is held at 150.degree.
C. for one hour and then heated at 190.degree. C. for 1 hour to
destroy any remaining di-t-butylperoxide. Then vacuum is applied to
the reactor and the unreacted maleic anhydride is removed. This
material is then diluted with a light neutral oil and filtered. The
product after filtration had a saponification number of 31.6 mg
KOH/g sample and contained 45.62 wt. % actives. The succinic ratio
was 1.5 for this material based on a polybutene molecular weight of
2200.
Preparation A
Preparation of Teta Polyisobutenyl (MN 2200) Succinimide (Succinic
Ratio=1.1)
(a) Succinimide
To a three neck flask equipped with an overhead stirrer, nitrogen
inlet tube and a Dean Stark trap was added 300.7 g PIBSA (SAP
no.=19.7 mg KOH/g sample, 0.0464 mol) that was prepared using the
procedure of preparation 2. To this was then added at 130.degree.
C. 3.39 g TETA with stirring. The mixture was heated for a total of
6.5 hrs. Then the reaction was cooled. A total of 0.8 ml water was
recovered. The analytical data for this compound is found in Table
1.
(b) Post treatment
Preparation of Ethylene Carbonate-Treated BIS TETA Polyisobutenyl
(Mn 2200) (Succinic ratio=1.1)
In this example 3.33 g ethylene carbonate (0.0378 mol) was added to
100 g of the BIS TETA Polyisobutenylsuccinimide from preparation A.
This was heated for 4 hours. Then the reaction was cooled to give
the title compound. The analytical data for this material is found
in Table 1.
Preparation B
Preparation of Heavy Polyamine Polyisobutenyl (MN 2200) Succinimide
(Succinic Ratio=1.1)
(a) Succinimide
To a 1 L three-necked flask equipped with a Dean Stark trap is
added 304.3 g (0.0469 mol) of PIBSA (SAP number=17.3mg KOH/g
sample), prepared using the procedure from Preparation 2. This is
heated to 130.degree. C. under nitrogen with stirring and to this
is added 6.45 g (0.02345 mol) of a heavy amine sold under the trade
name HPA-X, by Union Carbide Company over 0.5 hours. The
temperature was increased to 165.degree. C. The amine/PIBSA CMR was
0.5. The reaction is heated an additional 4 hours at 165.degree. C
while distilling off water. A total of 0.8 cc water was removed.
This product was analyzed and found to contain 0.82 %N, 16.6 TBN,
0.98 TAN, a viscosity at 100.degree. C. of 431.8 cSt and a specific
gravity at 15.degree. C. of 0.9149 The product contained about 40%
active material.
(b) Post-treatment
Preparation of Ethylene Carbonate-Treated BIS HPA-X Polyisobutenyl
(Mn 2200) (Succinic ratio=1.1)
In this example 7.4 g of ethylene carbonate is added over thirty
minutes to 100.5 g of Bis HPA-X PIBSA 2200 (succinic ratio=1.1) at
100.degree. C. The temperature of the reaction mixture is increased
to 165.degree. C. over 2.5 hours and then maintained at this
temperature for 2 hours affording the title compound.
Preparation C
Preparation of Polyalkylene Succinimide Using Deta, Pibsa 950, and
a C16 Alpha Olefin-maleic Anhydride Copolymer
To a 3 liter round bottom flask equipped with a magnetic stirrer,
Dean Startk trap, and nitrogen inlet was added 1950 g PIBSA 950 T
(1 mol), which had a SAP number of 57.5 mg KOH/g sample, and 1213 g
C.sub.16 alpha olefin/maleic anhydride copolymer (1.1 mol),
dissolved in C.sub.9 aromatic solvent, which had a SAP number of
102 mg KOH/g sample. The PIBSA 950 T/alpha olefin copolymer ratio
was 48/52. This was heated to 160.degree. C. and to this was added
over twenty five minutes, 108 g diethylene triamine (1.05 mole)
with stirring. The amine/PIBSA CMR was 0.5. After 2 hours heating,
the C.sub.9 aromatic solvent was then removed in vacuo. A total of
2460 g product was recovered, which had 1.69% N, and a viscosity at
100.degree. C. of 853.
Example 1
Preparation of Polymeric Succinimide Using Pibsa (MN 2200), HPA,
and C.sub.14 -C.sub.18 Alpha-Olefin Maleic Anhydride Copolymer
(a) Polymer
In this example, 658.4 (0.138 mol) of a polyisobutenyl (Mn 2200)
succinic anhydride having a succination ratio of 1.1 and a SAP
number of 23.6 mg of potassium hydroxide/g is added to a 2 L three
neck flask equipped with a Dean stark trap and condenser followed
by the addition of a solution of containing 59.5 g (0.059 mol) of a
C.sub.14 -C.sub.18 .alpha.-olefin-maleic anhydride copolymer in a
C-9 ml of a C.sub.9 aromatic solvent (a mixture of alkylbenzenes
having nine carbon atoms). The mixture is heated to 100.degree. C.
and 27.21 g (0.099 mol) of a heavy polyamine having an Mn of 275
containing an average of 6.5 amine nitrogen atoms per molecule sold
under the Tradename HPA-X by Union Carbide Company. The temperature
of the mixture is increased to 165.degree. C. and maintained at
this temperature for six hours with stirring. The C9 aromatic
solvent is then removed by vacuum distillation affording a viscous
liquid product having a nitrogen content of 1.21 wt. %, a TBN of
22.64 mg KOH/g, a TAN of 0.60 mg/g and a viscosity 440 cSt at
100.degree. C.
Example 1 EC
Ethylene Carbonite-Post-Treated Polymeric Succinimide of Example
1
33.06 g (0.376 mol) of ethylene carbonate is slowly added to 304.3
g of the above reaction product above at 100.degree. C. The
temperature is increased to 165.degree. C. and maintained at this
temperature for 31/2 hours. The resulting reaction product mixture
had a nitrogen content of 1.15 wt. %, a TBN of 15.9 mg KOH/g, a TAN
of 0.15 mg KOH/g and a viscosity of 812 cSt at 100.degree. C.
Example 2-6
Examples 2-6 are prepared following the same procedures as
described in Example 1 but varying the ratio of polyisobutenyl
succinic anhydride to copolymer based on succinic anhydride
equivalents or varying the particular polyamine but not the mole
ratio of polyamine; 0.5 moles of the indicated polyamine were added
per mole equivalent succinic anhydride in both the alkenylsuccinic
anhydride and maleic anhydride copolymer regardless of the
particular polyamine. The nitrogen content, TBN, viscosity, and TAN
number for these examples and Example 1 are reported in Table 1. In
addition, for comparative purposes, the Table also lists a
polyisobutenyl (Mn 2200) succinimide prepared by the same general
procedure as illustrated by Preparation A using either
triethylenetetraamine or heavy polyamine (HPA-X) and a mole ratio
of 0.5 mole of polyamine per mole of succinic anhydride and the
corresponding ethylene carbonite post-treated derivatives prepared
by the post-treatment illustrated by Preparation B. In each case
the polyisobutenylsuccinic anhydride reactant was prepared by the
thermal process using a conventional Mn 2200 polyisobutene such as
Parapol 2200.TM..
TABLE 1 ANALYTICAL DATA FOR POLYISOBUTENYLSUCCINIMIDE-MALEIC
ANHYDRIDE C.sub.14-18 OLEFIN COPOLYMER Example Mole Ratio.sup.1 N
TBN mg Vis. at TAN mg No. Amine PIBSA/Copolymer Wt. % KOH/g 1000C,
cSt KOH/g 1 HPA-X 70/30 1.21 22.6 440 0.6 1-EC HPA-X 70/30 1.15
15.9 812 0.15 2 TETA.sup.2 90/10 0.63 10.1 437 0.79 2-EC.sup.3 TETA
90/10 0.59 8.5 430 0.07 3 HPA.sup.4 -X 90/10 0.93 21.6 443 0.44
3-EC HPA-X 90/10 0.95 13.6 662 0.09 4 TETA 70/30 0.77 11.2 439 0.43
4-EC TETA 70/30 0.78 9.2 441 0.05 5 TETA 50/50 0.99 13.7 482 2.15
5-EC TETA 50/50 0.96 10.4 491 0.05 6 HPA-X 50/50 1.59 26.3 567 1.33
6-EC HPA-X 50/50 1.46 18.7 2676 0.07 COMPARISON PIB SUCCINIMIDES A
TETA 0.53 6.7 421 1.11 A-EC TETA 0.39 3.9 395 0.07 B HPA 0.82 16.6
432 0.98 B-EC HPA 0.76 8.8 599 0.09 C DETA 50/50 1.69 -- 854 --
.sup.1 Mole ratio of polyisobutenylsuccinic anhydride to copolymer
based on succinic anhydride units in each .sup.2
Triethylenetetraamine .sup.3 Ethylene carbonate treated .sup.4
Heavy polyamine sold under this Trade Name by Union Carbide
Company
Example 7
Preparation of Polymeric Succinimide Using Pibsa (MN 2200), HPA,
and a Styrene Maleic Anhydride Copolymer of Polyisobutylene (MN
2200) and Poly(Maleic Anhydride-styrene) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.6 mol of the same
heavy polyamine described in Example 1 to a mixture of 0.4 mol of
poly(maleic anhydride-styrene) copolymer and 0.6 mol of
polyisobutylene (Mn 2200) succinic anhydride having a succination
ratio of 1.1 at 100.degree. C. in a flask equipped with a Dean
Stark trap and condenser. The mixture is stirred at this
temperature for six hours. The mixture is then distilled under
vacuum to remove volatiles affording the title compound as the
principal product.
b) Post-treatment
The reaction product is then mixed with 0.76 mol of ethylene
carbonate for about four hours at about 160.degree. C. affording
the ethylene carbonate post-treated derivative of the title
composition.
Example 8
Tetraethylene Pentamine of Polyisobutylene (MN 2200) Succinimide
and Poly(Maleic Anhydride-ethylene) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.5 mole of
tetraethylene pentamine to a mixture of 0.7 mole of polyisobutylene
(Mn 2200) succinic anhydride having a succination ratio of 1.3 and
0.3 mol of poly(maleic anhydride ethylene) copolymer in 100 ml
(solvent) at 1000.degree. C. in a flask equipped with a Dean stark
trap and condenser. The mixture is stored at this temperature for 6
hours and then distilled to remove the solvent affording the title
compound as the principal product of the remaining mixture.
b) Post-treatment
0.71 mol of ethylene carbonate is added to the polymer reaction
product and heat at about 165.degree. C. for about four hours
affording the ethylene carbonate post-treated derivative of the
title compound.
Example 9
Polyamine of Polyisobutylene (MN 1300) Succinimide and Poly(Maleic
Anhydride-C.sub.24 .alpha. OLEFIN) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.5 mole of the same
heavy polyamine described in Example 1 to a mixture of 0.7 mole of
polyisobutylene (Mn 1300) succinic anhydride having a succination
ratio of 1.5 and 0.3 mol of poly(maleic anhydride C24
.alpha.-olefin) copolymer in 150 ml (C.sub.9 aromatic,
cholorobenzene, toluene or dioxane solvent) at 100.degree. C. in a
flask equipped with a Dean stark trap and condenser. The mixture is
stored at this temperature for 6 hours and then distilled to remove
the solvent affording the title compound as the principal product
of the remaining mixture.
b) Post-treatment
0.71 mol of ethylene carbonate is added to the polymer reaction
product and heat at about 160.degree. C. for about four hours
affording the ethylene carbonate post-treated derivative of the
title compound.
Example 10
Polyamine of Polyisobutylene (MN 2200) Succinimide and Poly(Maleic
Anhydride-1,3-Butadiene) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.5 mole of the same
heavy polyamine described in Example 1 to a mixture of 0.6 mole of
polyisobutylene (Mn 2200) succinic anhydride having a succination
ratio of 1.1 and 0.4 mol of poly(maleic anhydride-1,3-butadiene)
copolymer in 50 ml (chlorobenzene) at 100.degree. C. in a flask
equipped with a Dean stark trap and condenser. The mixture is
stored at this temperature for 6 hours and then distilled to remove
the solvent affording the title compound as the principal product
of the remaining mixture.
b) Post-treatment
0.71 mol of ethylene carbonate is added to the polymer reaction
product and heat at about 165.degree. C. for about four hours
affording the ethylene carbonate post-treated derivative of the
title compound.
Example 11
Polyamine of Polyisobutylene (MN 1300) Succinimide and Poly(Maleic
Anhydride-methyl Vinyl Ether) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.5 mole of the same
heavy polyamine described in Example 1 to a mixture of 0.8 mole of
polyisobutylene (Mn 1300) succinic anhydride having a succination
ratio of 1.1:1 and 0.2 mol of poly(maleic anhydride-methyl vinyl
ether) copolymer in 200 ml n-methyl pyrrolidone at 100.degree. C.
in a flask equipped with a Dean stark trap and condenser. The
mixture is stored at this temperature for 6 hours and then
distilled to remove the solvent affording the title compound as the
principal product of the remaining mixture.
b) Post-treatment
0.71 mol of ethylene carbonate is added to the polymer reaction
product and heat at about 170.degree. C. for about four hours
affording the ethylene carbonate post-treated derivative of the
title compound.
Example 12
Polyamine of Polyisobutylene (MN 2200) Succinimide and Poly(Maleic
Anhydride-vinylacetate) Copolymer
a) Polymer
The title compound can be prepared by admixing 0.5 mole of the same
heavy polyamine described in Example 1 to a mixture of 0.5 mole of
polyisobutylene (Mn 2200) succinic anhydride having a succination
ratio of 1.1:1 and 0.5 mol of poly(maleic anhydride-vinylacetate)
copolymer in 200 ml dimethyl fluoride at 100.degree. C. in a flask
equipped with a Dean stark trap and condenser. The mixture is
stored at this temperature for 6 hours and then distilled to remove
the solvent affording the title compound as the principal product
of the remaining mixture.
b) Post-treatment
0.71 mol of ethylene carbonate is added to the polymer reaction
product and heat at about 170.degree. C. for about four hours
affording the ethylene carbonate post-treated derivative of the
title compound.
Example 13
Lubrication Oil Dispersancy
The effectiveness of the compositions reported in Table I as was
determined by the Panel Coker Bench Test and by the Soot Thickening
Test. The results of this testing are reported in Table III.
1. Panel Coker Bench Test
In this test 200 g of the lubricating oil composition being tested
is weighed into a 400 ml beaker. The test composition is a mixture
of containing 8 wt. of the dispersant to be tested, 36 millimoles
of an overbased phenate detergent and 18 millimoles of a zinc
dithiophosphate wear inhibitor in Citcon.RTM. 350 N diluent oil. To
this is added 0.2 ml of a catalyst solution. The catalyst solution
consists of a mixture of 62.12 g of copper naphthenate solution
(7.88 wt. % copper) and 48.04 g iron naphtenate (6.12% iron)
dissolved in pearl oil to 200 ml. This gave a copper content of 25
ppm and an iron content of 15 ppm in the oil. The oil and catalyst
solution then stirred together for one minute. The test composition
is then poured into the sump of the panel coker apparatus and a new
plate (weighed to 0.0001 g) is installed. The following conditions
are used for the panel coker test. The plate temperature is
300.degree. C., the sump temperature is 18.degree. C., the run time
is 4 hours, the air flow rate is 60 cc/min. During the test the
spinner is on for 12 seconds then off for 78 seconds. During the
time the spiner is on the test composition is splashed onto the
plate. Then with the spinner off, the test composition slowly
drains off the surface of the plate. The spinner on/off cycle is
continued for 4 hours after which time the plate was removed,
rinsed with hexane and dried. The plate is weighed to 0.0001 g and
the weight gain is reported as weight of total deposit. Thus the
lower the weight the better the result.
2. Soot Thickening Test
In this test 98.0 g of the test lubricating oil composition is
weighed and placed into a 250 milliliter beaker. The lubricating
oil composition contained 8 wt. % on as is basis of the test
dispersant 50 millimoles of an overbased phenate detergent, 18
millimoles of a zinc dithiophosphate wear inhibitor and 7.3 wt. %
of a VI improver, in 85% 150N oil, 15% 600N oil. To this is added
2.0 g Vulcan XC-72R.TM. carbon black from Cabot Co. The mixture is
stirred and then stored for 16 hr in a desiccator. A second sample
of the lubricating oil composition, but without the carbon black,
is mixed for 60 sec. using a Willems Polytron Homogenizer--Model PF
45/6 and then degased in a vacuum oven for 30 minutes at
50-55.degree. C. The viscosity of the two test compositions is then
measured at 100.degree. C. using a capillary viscometer. The
percent viscosity increase is calculated by comparing the viscosity
in the presence and absence of carbon black. Thus the lower the
percent viscosity increase the better the dispersancy of the
dispersant.
TABLE III DISPERSANCY PANEL COKER AND SOOT THICKENING Polyamine
Mole Rate Panel Coker, Soot Thickening, EXAMPLE No. Description
PIBSA/Copolymer mg % Vis. Incr. 1 Bis HPA 70/30 156.8 117 1 EC EC
Bis HPA 70/30 61 24 2 Bis TETA 90/10 4 295 2 EC EC Bis TETA 90/10
13.4 87 3 BIS HPA 90/10 29.4 146 3 EC EC Bis HPA 90/10 4.3 25 4 Bis
TETA 70/30 66.6 191 4 EC EC Bis TETA 70/30 71.2 36 5 Bis TETA 50/50
120.2 173 5 EC EC Bis TETA 50/50 311.7 37 6 Bis HPA 50/50 299.9 48
6 EC EC Bis HPA 50/50 311.7 30 COMPARISON SUCCINIMIDES A TETA 10.7
345 PIBSA 2200T A-EC TETA -- -- PIBSA 2200T B HPA 7.5 310 PIB8A
2200T B-EC HPA -- -- PIBSA 2200T
Example 14
Sequence VE Engine Test
The ethylene carbonate treated reaction product of Example 1EC was
formulated into a lubricating oil composition with a mixture of
150N and 100N mineral oil at a concentration of 5.3 wt. % (based on
the reaction product mixture). The lubricating oil composition also
contained small amounts of phenate and sulfonate detergents, a zinc
dithiophosphate wear inhibitor and a viscosity index improver such
as conventionally used in passenger car crankcase lubrication
oils.
The dispersant performance of the composition was tested using the
Sequence VE Engine test procedure defined in ASTM proposed Method:
212. This test assesses a lubricant's ability to provide adequate
wear and deposit control under stop-and-go conditions. The test
measures rocker cover sludge ("RCS"); average engine sludge
("AES"), piston skirt varnish ("PSV"); average engine vanish
("AEV") average cam wear ("ACW"), and maximum cam wear ("MCW").
The results of this testing is shown in Table IV. The pass limits
for each performance measure is also indicated in the table. As can
be seen from the table, with the exception of example C which
contains a 950 molecular weight polybutene tail, the lubricating
composition passed each performance measure.
TABLE IV Example No. RCS AES PSV AEV ACW MCW 1 EC 9.17 9.15 7.20
6.84 1.12 1.00 Pass Limits 7.00 9.00 6.50 5.00 5.00 15.00 (min.)
(min.) (min.) (min.) max in (max in mils) mils) B-EC 8.56 9.15 7.17
6.55 0.89 1.25 C 1.9 4.8 6.6 4.7 5.0 11.2
While the present invention has been described with reference to
specific embodiments, this application is intended to cover those
various changes and substitutions that may be made by those skilled
in the art without departing from the spirit and scope of the
appended claims.
* * * * *